TW558558B - Microgel synthesis - Google Patents

Abstract

The invention provides in one aspect a process for preparing a microgel by RAFT polymerizing in the presence of a RAFT chain transfer agent, one or more solvophobic monomers and one or more solvophilic monomers to form one or more block copolymers comprising one or more solvophobic blocks and one or more solvophilic blocks wherein the solvophobic block is insoluble in a dispersing medium and the solvophilic block is soluble in the dispersing medium. The block copolymer is dispersed in the dispersing medium to form micelles, which is then stabilized to form the microgel. The dispersing medium can be aqueous or lipophilic. The method of the present invention also permits one to encapsulate a wide variety of materials, such as pigments, dye molecules, and aluminum flakes used in metallized paints.

Description

558558 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) Technical scope The present invention relates to a method for preparing microgels or crosslinked micelles and encapsulating pharmaceutical agents in the micelles. Microgels produced by the method and products containing such microgels. if! background Sub-micron-sized microgels are also called "nanospheres". The properties of microgels make them useful in a wide range of applications, such as additives, foaming agents or advanced ingredients for fibers, adhesives, and redispersible polymers. Diblock (AB) and triblock (A_B-A) copolymers are generally formed in a detergent when one of the block components is soluble (miscible) and the other is not soluble or immiscible (immiscible). Micelle. There are many examples of this type, such as block copolymers with sizing agent poly (phenylene fluorene) blocks and solvophilic poly (ethyl fluorene oxide) blocks that form micelles in alcoholic solvents. Solventophilicity_Solventphobicity balance W Xiangxin segment natural tendency to form micelles. In order to realize the micelle effect, it is sometimes possible to first dissolve the block copolymer in a mutual solvent, and then disperse the solution into a block of insolvent, or change the solvent to insolvent ratio. The size of the micelles obtained depends on the molecular weight and solvent properties of the component blocks. Micelles are dynamic systems that are balanced between block copolymer micelles and non-micellar forms. In order to stabilize polymerizable micelles, it is necessary to chemically modify the micelles formed to stabilize them into the desired configuration. Crosslinking reactions are generally used. The micelles can be stabilized by core or shell crosslinking. Because the reactive groups present in these systems can react with each other to generate difficult-to-control networks, microgels need to be prepared with care. The cross-linked micelles based on the copolymers raised by Nai and You are especially well-known. -4- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page) ----- Installation -------- Order --- ------ · 558558

5. Description of the Invention () and Y00) are disclosed in US Patent No. 5,429,826. Various shell-crosslinked micelles based on block copolymers were disclosed by Wooie et al. In WIPO Patent No. 97/49387, the disclosure of which is incorporated herein by reference. These reveal that the block copolymers used are synthesized by anionic or group transfer polymerization. These methods have several disadvantages. These methods are implemented at high cost. Moreover, only a narrow range of monomers is allowed. The use of these techniques must protect protonic monomers (eg, methylpropionate) and remove the protection before micelles. Anionic and group transfer polymerizations cannot generally be used to produce copolymer blocks. These conditions severely limit the range of block copolymers used to generate micelles. Crosslinked micelles can also be prepared as described by Saito et al. (J Appl Polym, Sci ·, 1997, 63, 849), using a dithioamino formate (salt) photoinitiator to free Block copolymers synthesized by radical polymerization, or block copolymers synthesized by atom transfer polymerization as disclosed by Armes (J. Am. Chem. Soc. 1999, 121, 4288). These block copolymer synthesis methods also have disadvantages and can only be applied to a very narrow range of monomers. Recently, World Intellectual Property Organization Patent No. 98/01478 describes a novel method for synthesizing various block copolymers. This method is based on the application of a chain transfer agent and is synthesized by free radical polymerization through a reversible addition-cracking chain transfer (RAFT) reaction. Block copolymer. These reactants provide an economic path for block copolymers derived from different ranges of monomers. · Preferred chain transfer agents for these methods include thiocarbonylthio compounds (dithioesters, trithiocarbonates (salts), xanthates (salts) and dithiocarbamates (salts) ) And some macromonomers. A particular advantage is that acid-containing monomers can be polymerized without a protection-deprotection strategy. Reactive functional groups that allow cross-linking can also be incorporated. -5- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) • · · ϋ ϋ «ϋ n · ϋ n · ϋ ον I华 ϋ n Hua. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 558558 A7 B7 V. Description of the invention (Now the present invention recognizes that 'block copolymers produced by RAFT polymerization are beneficial for generating micellar structures, thereby avoiding and generating Some problems related to the prior art methods of cross-linked micelles. # The present invention also recognizes that particle encapsulation of a third group of molecules or particles with micellar stabilization is very useful, and these are used as microgels for stabilization Micelles can also be modified by arm chain growth after preparation. The advantage of the method of the present invention is that it can have a relatively wide range of functions, such as cross-linking functions, controlling surface functions, and determining the microenvironment in the micelle core. DESCRIPTION OF THE INVENTION 1. The present invention In one aspect, a method for preparing a microgel is provided, which comprises: (i) RAFT polymerizing one or more solvotropic monomers and one or more solvophilic monomers in the presence of a chain transfer agent to produce One or more block copolymers comprising one or more solvophobic blocks and one or more lyophilic blocks, and wherein the solvophobic blocks are insoluble in the dispersion medium and the solvent Blocks are dissolved in the dispersion medium; (ii) disperse the segment copolymer into micelles in the dispersion medium; and (iii) stabilize the micelles into microgels. The present invention also recognizes that novelty can be generated Can stabilize the micelle structure, which contains one or more of the following functional groups: —i -------- 衣 -------- Order --------- (Please read the back Please fill in this page again for attention) Print an appropriate ruler on paper

¾ Male 97 2 X-10 2 / V Gage A4 S) N (C Associate Standard 558558

cn

• CH, one C ^ CH2

X CHf p wherein R, Z, x, and p are as defined below, and the present invention includes stabilized microgels produced by these micellar structures. Where 'R, Z, X and p are as defined below, and the present invention includes stabilized microgels produced by these micellar structures. Certain block copolymers used in the present invention are novel compounds and also form part of the invention. Another aspect of the present invention provides a method for preparing a microgel, comprising: providing one or more crosslinkable block copolymers selected from the following compounds: ---.-------- pack --- ----- Order · (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

P This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 558558 A7 V. Description of the invention (κ ζ

s—ν -υ-R

Vila

H2C '

CH2 * ν · ~ -υ— · ρ XVilla Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where R'R1 and P are free radicals; and where R is selected from the group consisting of the following groups: Unsubstituted or substituted C 1 to C 1 s fluorenyl, unsubstituted or substituted diluent, unsubstituted or substituted block, unsubstituted or substituted * saturated carbocyclic ring, unsubstituted or substituted Substituted unsaturated carbocyclic ring, unsubstituted or substituted aromatic carbocyclic ring, unsubstituted or substituted saturated heterocyclic ring, unsubstituted or substituted A unsaturated heterocyclic ring, unsubstituted or substituted aromatic heterocyclic ring, Unsubstituted or substituted alkylthio and a first polymer chain having a number average polymerization degree of 5 to 1000; Z is selected from the group consisting of hydrogen, gas, unsubstituted or substituted C i To Ci 8 alkyl, unsubstituted or substituted aryl, unsubstituted or substituted C 3 to Ci 8 heterocyclic ring, unsubstituted or substituted Ci to ci 8 alkylthio, SR, unsubstituted Substituted or substituted arylthio, unsubstituted or substituted Ci to Ci 8 alkoxy, unsubstituted or substituted aryloxy, unsubstituted or substituted 8-t paper size is applicable to China National Standard (CNS) A4 (210 x 297 mm) i ---------- installation -------- order -------- -Line (please read the notes on the back before filling this page) 558558 A7 6 V. Description of the invention (Substituted amine group, unsubstituted or substituted C i to C 1 8 alkoxycarboxyl group, unsubstituted or substituted aromatic Oxocarbonyl, carboxyl, unsubstituted or substituted Ci to Ci8 fluorenyloxy, unsubstituted or substituted arylfluorenyloxy, unsubstituted or substituted carbamoyl, cyano, c2 to c18 dioxane Phosphonic acid group, diarylphosphonic acid group, (: 1 to (: 18 dialkylphosphinic acid group, diarylphosphinic acid group) and a second polymerization having a number average degree of polymerization of 5 to 10,000 Bond; R1 is the η-valent moiety derived from R; Z 1 is the η-valent moiety derived from the group selected from the following groups: unsubstituted or substituted C! To Ci8 alkyl, unsubstituted Or a substituted aryl group and a third polymer chain having a number average degree of polymerization of 5 to 1,000, wherein the connecting part of the polymer chain is selected from the group consisting of ci to ci 8 aliphatic carbons, aromatic carbons, oxygen, sulfur, and combinations thereof Group; P is homogeneous with 2 to 1000 numbers Oligomer or polymer with a degree of conformity or the first polymer chain; X is selected from the group consisting of: unsubstituted or substituted aryl, Ci to Ci 8 alkoxycarbonyl, unsubstituted or modified Substituted aryloxycarbonyl, carboxyl, unsubstituted or substituted aryloxycarbonyl, carboxyl and cyano; η is an integer from 1 to 6; and wherein R, R1, Z, Z1 and X are substituted The substituents of the group are independently selected from the group consisting of: hydroxyl, tertiary amine, pixel, cyano, epoxy, carboxylic acid, alkoxy, alkyl having 1 to 32 carbon atoms , Aryl, alkenyl with 2 to 32 carbon atoms, alkynyl with 2 to "carbon atoms, saturated carbocycle with 3 to 14 carbon atoms, unsaturated carbocycle with 3 to" carbon atoms, Aromatic carbon rings with 6 to 14 carbon atoms, 3 to 14 paper sizes Applicable to China National Standard (CNS) A4 specifications (210 X 297 mm factory—AVI -------- Order --- ------ (Please read the notes on the back before filling in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 558558 Α7 Β7 V. Description of the invention () Saturated miscellaneous carbon atoms 3. Unsaturated heterocyclic rings with 3 to 14 complete atoms, aromatic carbon (hetero) rings with 3 to 14 carbon atoms; or • When Z is -SR, the copolymer should have the following structure: S —U—v—RS—U—V—R or S: printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where: U and V are block copolymers that are immiscible under the conditions selected by micelle action, and the When the block copolymer is placed under these conditions, it will aggregate itself to form micelles or micelle aggregates or dispersions; and each R may be the same or different. U and V are best selected together: u is poly (butyl methacrylate-co-fluorenyl allyl acrylate) -insert-poly (butyl methacrylate), V is poly (methacrylic acid) ; Υ is poly (hydroxyethyl methacrylate-co-methacrylic acid 2-ethylhexyl-co-isopropyl methylpropionate) V is poly (acrylic acid-co-methyl methacrylate_co. · Methyl acrylate_co-phenethylhydrazone); and U is poly (hydroxyethyl methacrylate-co-ethyl 2-hexyl methacrylate-co-fluorenyl isobutyrate) V is poly (Glycidyl acrylate-co-methyl methacrylate-co-methyl acrylate-co-styrene). -10 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Γ -I 0 I nnn ϋ · ϋ ϋ 口 口, 9 · ϋ ϋ ϋ # · 558558 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, A7. 5. Description of the invention (The other aspect of the present invention provides microgels generated from different aspects of the present invention. The present invention further provides a method for encapsulating materials into microgels. It includes, before or after the micelle action, adding a partially solubilized suspension of the material to the above-mentioned dispersion of the block copolymer to stabilize the micelles to generate a microgel that encapsulates the material. Invention W A detailed description of the definition herein: "block copolymer" refers to the structure of the formula [A (B) n] m, where n * m is an integer, A and B are homopolymers or statistical copolymers, or they are block copolymers themselves "RAFT polymerization" refers to a method in which a chain transfer agent is used to carry out radical polymerization from a reverse addition cleavage chain transfer reaction to synthesize a block copolymer. The micellar structure "refers to a heterogeneous particle structure assembled by itself. '' Initiation Radical "means from a radical source The radical type is generated and a monomer group is added to generate a radical. `` Propagation group '' means a radical type to which one or more monomer units have been added and other monomer units can be further added. `` Stabilization '' Or other forms of the word refer to the modification of the micelles produced to fix the desired configuration, including chemical modification of the micelles by crosslinking and / or chain growth. The "degree of polymerization" of a block is the number of repeating units of the monomer in the block. The "polydispersity" of a polymer is the ratio of the weight-average degree of polymerization to the number-average degree of polymerization. "Polymer particle size" refers to Malvern Zetasizer 4 [from Uster, UK Xia, Melvin, polymer particle diameter provided by Malvern Instrument Corporation (Malvern Instrument Corporation, Malvern, Worcs, UK)]. The instrument uses 5 milliwatt He-Ne633 nano-11 This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) --- * ------- install -------- order --------- (Please read the precautions on the back first Refill this page} 558558 A7 B7 V. Description of the invention (9 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Mi laser operation uses quasi-elastic light scattering technology to measure polymer particle size. The scattering intensity is a function of particle size. This technology was described by Weiner et al. (Ai ^ rican Society, 1987 edition) Symposium), Chapter 3, page, titled "Application and Misuse of Photon Correlation Spectroscopy in Particle Sizing" (仏 ㈡—Edit ... Of Photon Correlation Spectroscopy in Particle Sizing) 〇 is the particle size of T, About 2 liters of sample solution was transferred to the quartz cell and placed in the instrument. Particle size (in nanometers) is then measured using standard test settings. Repeat the measurement twice to ensure consistency. The particle distribution is reported based on a particle size relative to 2 particles. The size of the microgel particles depends on the molecular weight of the subsequent copolymer, its composition, concentration, and dispersion medium, and is selected according to the intended use of the microgel. The diameter can be larger, and the particle diameter is more preferably 20 nm to 100 nm. The microgel may contain two or more dispersed phases resulting from phase separation of the spent copolymer during the stabilization step. RAFT chain transfer agents for use in the present invention are familiar to us. Some examples of these RAFT agents are disclosed in WIPO Patent No. 99/3 丨 144, the contents of which are incorporated herein by reference. In forming a crosslinkable block copolymer for use in the present invention, preferred chain transfer agents used include thiocarbonylthio chain transfer agents of formula IIII and macromonomers of formula IV. ZZ

S—R s == (1 -R · _ * 1 S > ZL _ η R—SL _ II ΠΙ -12- < Zhang scale is applicable to China National Standard (CNS) A4 specification (210 X 297) (Please Read the precautions on the back before filling this page) ▼ -install -------- order --------- line win • Z 558558 A7 V. Description of the invention (Corpse 2 P-CHa-c7 (Please read the notes on the back before filling this page)

X

IV where R'R1 and P are free radical leaving groups; where R is selected from the group consisting of: 4 substituted or substituted alkyl groups, unsubstituted or substituted alkenyl groups , Unsubstituted or substituted alkynyl, unsubstituted or substituted saturated carbocyclic ring, unsubstituted or substituted unsaturated carbocyclic ring, unsubstituted or substituted aromatic carbocyclic ring, unsubstituted or substituted saturated heterocyclic ring Ring, unsubstituted or substituted saturated heterocyclic ring, unsubstituted or substituted aromatic heterocyclic ring, unsubstituted or substituted alkylthio group and having 5 to 1000, preferably 5 to 100 and more preferably 5 to 50 The first polymerization chain with a uniform degree of polymerization;-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Z is selected from the group consisting of hydrogen, gas, unsubstituted or substituted C 1 to C i8 , Unsubstituted or substituted aryl, unsubstituted or substituted C3 to ci8 heterocycle, unsubstituted or substituted c! To ci 8 thiothio, SR, unsubstituted or substituted arylthio, Unsubstituted or substituted Ci to C! 8 alkoxy, unsubstituted or substituted aryloxy, unsubstituted or substituted amine , Unsubstituted or substituted Ci to Ci 8 alkoxycarbonyl, unsubstituted or substituted aryloxycarbonyl, thiol, unsubstituted or substituted ci to ci 8 donkeyoxy, unsubstituted or substituted Substituted aromatic acidoxy, unsubstituted or substituted carbamoyl, cyano, c2 to c18 dialkylphosphine 'acid group, diarylphosphonic acid group, (: 1 to (: 18 dialkylphosphine) Acid group, diarylphosphinic acid group, and the second polymerization with an average polymerization degree of 5 to 1000, 5 to 100 and better 5 to 50, 13- This paper size applies to China National Standard (CNS) A4 specifications ( 210 X 297 mm) 558558 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention () Chain; R1 is derived from the η-valence portion of R; ZO1 is derived from the group selected from the following groups Valence part: unsubstituted or substituted Ci to Ci 8 alkyl group, unsubstituted or substituted aryl group, and a third polymerization chain having a number average polymerization degree of 5 to 1,000, wherein the polymerization chain is The linking moiety is selected from the group consisting of ci to Ci 8 aliphatic carbons, aromatic carbons, oxygen, sulfur, and combinations thereof; P is a compound having 2 to 1000 (compared with Preferably 2 to 100, more preferably 2 to 50) an oligomer or polymer having a number-average degree of polymerization or the first polymer chain; X is selected from unsubstituted or substituted aryl groups, (: 1 to (:; A group of 18 alkoxycarbonyl, unsubstituted, star-substituted or substituted aryloxycarboxyl groups, carboxyl groups, unsubstituted or substituted aryloxycarbonyl groups, CiSCi8 carboxyl groups, and cyano groups; η is an integer from 1 to 6; And the substituents of the substituted groups of R, R1, Z, Z1, and X are independently selected from the group consisting of the following groups: Wei group, tertiary amino group, # prime, cyano group: epoxy group , Carboxylic acid, fluorenyloxy group, alkynyl group with U32 carbon atoms, alkenyl group with 2 to 32 carbon atoms, alkynyl group with 2 to 32 carbon atoms, saturated carbon with 3 to 14 carbon atoms Ring, unsaturated carbocyclic ring with 3 to "carbon atoms, aromatic carbocyclic ring with 6 to 14 carbon atoms, saturated heterocyclic ring with 3 to 14 carbon atoms, unsaturated heterocyclic ring with 3 to 14 strong atoms Ring, aromatic carbon (hetero) ring with 3 to 14 carbon atoms. The "polymeric chains" mentioned for R, R1, ζ, ζι and p refer to conventional condensation polymers such as polyesters [e.g. tcaprolactone, polyethylene terephthalate lactic acid], poly Carbonic acid vinegar, osmium oxide (polyethylene glycol M, for example, polyethylene oxide-14) This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) — * -------. AW— -------- Order --------- (Please read the notes on the back before filling out this page) 12 12 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as 558558 5 2. Description of the invention (（, poly (1,4-butanediol)] Nilen (compound [such as by coordinating poly φ fluorenyl methylbismuth ester or chain poly (such as poly (meth) acrylic acid vinegar And polystyrene residues = 1), phase-based polymerization ^ and polybenzyl series ^ anionic polymerization (such as polyethylene, polybutadiene), impotence yw M j ^; field ion polymerization (such as polybutylene (Eg, poly-f-A, di-A, O //, Ding 埽) and the group methyl) propionate version @ 旨) should choose the group R, R1, 2 and 7 !, You > and m Z make < common to the required monomer or single month Mixture and international patent public land w dry f ⑺ a σ W〇98 / 01478, WO99 / 〇5〇99 Ancient, and Tuganshi ~ Women as disclosed in WO 99/3 1144. Manfa, within Gujun is cited by reference and the AFT I block copolymer can be used in emulsion, solution or suspension in batch, semi-batch, continuous or feed mode. For lower polydispersity, polymer Generally, the RAFT reactant is added before the polymerization is started. For example, when carried out in a batch manner in a solution, the reactor is generally charged with 1 1 1 agent and monomer, or the polymerization medium and monomer are added. The polymerization process is controlled by the addition of RAFT agent, which results in a broader, but controlled polydispersity or multimodal molecular weight distribution block copolymer. In the case of emulsion or suspension polymerization, the polymerization medium is often mainly water and may exist Custom stabilizers, dispersants, and other additives. For solution polymerization, a wide range of media can be selected to suit the monomer polymerization media used. For example, 'aromatics, such as naphtha (petroleuninaphtha) or toluene; ketones, such as formazan Pentyl ketone, methyl Butyl ketone, fluorenyl · ketone or acetone; esters such as butyl acetate or hexyl acetate; glycol ether esters, propylene glycol acetate monomethyl ether. Use of feed polymerization conditions allows the use of RAF T with lower chain transfer constants剂 -15- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------- # 丨-装 -------- Order ------- -. (Please read the precautions on the back before filling out this page) 13. Description of the invention (= compound = block copolymer that is not easy to obtain by batch polymerization method). If the second is performed as a feed system, the reaction can be performed as follows. (Please read the precautions on the back before filling out this page) Shijiao — Han AFT agent and selected monomer mixtures fill the reactor. The rest of the monomer mixture a. Dissolve the free-radical initiator in ... alone ... In the grain container, ^, 蟋, and 蟋 are in the polymerization medium. Introduce the medium in the reactor: two, and stir it and introduce it into the monomer mixture plus the medium to initiate the addition of the lean medium, such as a syringe pump or other delivery device. The feed rate and time are 1 point higher depending on the amount of solution, the required monomer / fluorene T agent / initiator ratio, and the polymerization rate. When the feed is complete, heating can be continued for an additional period of time. After 70% of the polymerization, the medium and unreacted monomers can be removed, or the copolymer in the subsequent stage can be separated with an insoluble solvent. Alternatively, the polymer solution / emulsion can be used as is if it is suitable for the application. Block and multi-block and gradient copolymers can be prepared by changing the rate of monomer addition and / or the order in which monomers are added to the polymerization medium. Gradient blocks can also be prepared in one step using the reactivity differences of the monomers themselves. For gradient block copolymers, it is often necessary to select comonomers based on different reaction ratios. Examples are maleic anhydride and phenethylhydrazone or (meth) acrylates. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the group R, R1, Z, Zi, P, and X of the RAFT chain transfer agent of the above formula I · ΐν, which can easily generate a block with a clear terminal functional group. Copolymer. To prepare a block copolymer, one can start with an existing polymer chain prepared by a method other than RAFT polymerization, modify its ends or other functional groups, and incorporate the polymer chain into a compound of formula I-IV to produce a chain that can grow by RAFT polymerization. Macromolecular RAFT agent. The "free radical source" or initiator suitable for the present invention includes the provision of added to the monomer production -16-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 558558 A7

V. Description of the invention (14) The compound produced by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is a bio-based initiator. The amount of initiator depends on the desired polydispersity, molecular weight, and polymer structure of the polymer produced. However, it is generally less than 10% by weight based on the total amount of the monomer mixture. The amount of the initiator used is preferably from 0.001 to 50% by weight. Initiating sources include the following sources: thermally induced homolytic initiators, such as peroxides, peracetates, or azo compounds; spontaneously generated from monomers, such as styrene; redox initiation systems, photochemical initiation systems, or high-energy radiation Source, such as electron beam X- or r-radiation or a combination of these methods. These systems should be selected so that the initiator or initiator does not adversely affect the RAFT agent under the reaction conditions. The initiator should also have the necessary solubility in the reaction medium or monomer mixture. Examples of suitable free radical sources for the process include azo compounds and peroxides, such as: 2,2 '· azobis (isobutyronitrile), 2,2, _azobis (2-cyanobutane) , Dimethyl 2,2'-azobis (methyl isobutyrate), 4,4, -azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyano -1-pentanol), 1,1, _azobis (cyclohexanecarbonitrile), 2- (third butylazo) -2-cyanopropane, 2,2, -azobis [2- Fluorenyl-N- (l, l) -bis (hydroxyfluorenyl) -2-hydroxyethyl] propanamide, 2,2, -azobis [2 · methyl_N-hydroxyethyl] propanium Amine, 2,2'-azobis (11 ^,-dimethylmethylene isobutyrium) dihydrochloride, 2,2, azobis (2-fluorenylpropane) dihydrochloride, 2,2 '-Azobis (^^ 山' _dimethylene isobutylamidine), 2,2'-azobis (2-methyl- > ^-[1,1-bis (hydroxymethyl)) -2-Hydroxyethyl] propanamide), 2,2'-Azobis (2-methyl-N- [l, l_bis (hydroxymethyl) ethyl] propanamine, 2,2 ' -Azobis [2-methyl-N- (2-hydroxyethyl) propanamidin], 2,2'-azobis (isobutylamidamine) dihydrate, 2,2'-azobis (2,2,4-trifluorenylpentane) 、 2,2'-azo-17- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ▼ — · ----------------------- Order --------- Line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 558558 A7 ___B7 V. Description of the invention (15) Double (2_methyl propyl) Burning), third butyl peracetate, third butyl perbenzoate, third butyl peroctoate, third butyl perdecanoate, third butyl perisobutyrate, third butyl pervalerate Esters, tert-butyl perpivalate, diisopropyl percarbonate, dicyclohexyl percarbonate, dicumyl peroxide, diphenyl peroxide, dilaurate, dipersulfate , Perdisulfate, di-tertiary butyl nitrate, or dicumyl dinitrate. The photochemical initiator system should be selected to have the necessary solubility in the reaction medium or monomer mixture under the polymerization conditions. Appropriate quantum yield for the generation of free radicals. Examples include benzoin (benzophenone) derivatives, benzophenones, phosphonium oxides and photochemical redox systems Free radicals can also be derived from the direct actinic action of compounds of formula ι_ΠΙ. The redox initiator system should be selected so that it has the necessary solubility in the reaction medium or monomer mixture and has the appropriate free radical yield under the polymerization conditions; The system may include a mixture of the following oxidants and reducing agents: Oxidizing agents: potassium persulfate, hydrogen peroxide, and third butyl hydrogen peroxide. Reducing agents: iron (11), titanium (111), potassium thiosulfite, and Other suitable priming systems are described in the recent monographs. For example, Moad and Solomon " Free Radical Polymerization Chemistry "

Chemistry of Free Radical Polymerization), Pergamon, London, 1995, pp. 53-95. The monomer mixture used in the RAFT polymerization process may include at least one vinyl monomer of the following formula (IX): -18- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --- * ------- I Zhuangyi -------- Order · -------- (Please read the notes on the back before filling this page) Preparation 558558 A7 B7 V. Description of the invention (16) CH2 = rc ^ Μ χ, where L is a substituent selected from the group consisting of hydrogen, halogen, and substituted or unsubstituted C 1 -C 4 alkyl groups and alkyl groups Is independently selected from the group consisting of Ο Η, 0 R ”, Co 2H, OAR”, Co 2r ”and combinations thereof; and wherein M is selected from the group consisting of hydrogen, r”, co 2h, Co 2R ,, COR ", CN, CONH2, CONHR", coon "2: 0 2 CR", 〇R ", and self prime. R 'is selected from the group consisting of the following groups: Substituted or unsubstituted pit, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aralkyl, substituted or unsubstituted Substituted alkanes Or a combination thereof. Depending on the type of block copolymer desired, the monomer mixture may also include the following monomers:-maleic anhydride, N-alkylmaleimide, N-arylmaleimide Imine, fumaric acid, dimerization, ring-polymerizable or ring-opening monomer or a mixture thereof. The monomer mixture may also include a macromonomer (where L or μ is a polymer chain) which is a compound of formula (IX.) ) 0 The monomer or comonomer of formula (XI) generally includes one or more of the following monomers: acrylates and methacrylates, acrylic and methacrylic acid, styrene, acrylamide, methacrylamide , Acrylonitrile, methacrylonitrile, -19- this paper rule Yuncai 0 national standard (CNS) A4 specification (210 X 297 public love) " --- ^ I -------- ^- ------- (Please read the precautions on the back before filling out this page) 558558 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (17 Mixture of vinyl ester and these monomers and A mixture of these monomers with other monomers. Those skilled in the art should recognize that the choice of comonomers is determined by their temporal and electronic properties. Decide not to The factors of copolymerization with homo-monomers are technically proven. For example, Greenley, RZ, Polymer Handbook, Third Edition [Brandup J, and Emogert ( Immergut), EH. Publishing], New York: Wiley: New York 1989 p II / 53. The explicit monomer or comonomer of formula (XI) includes one or more of the following compounds: methacrylic acid Methyl esters, ethyl methacrylates, propyl methacrylates (all isomers), butyl methacrylate (all isomers), methyl ethyl propionate octaethylhexanoate, ethyl isopropyl acrylate Borneol g purpose, methylpropionate, methacrylic acid g purpose, methacrylic acid benzene g purpose, methacrylonitrile, α-methylacetophenone, methyl acrylate g purpose, ethyl propionate Esters, propyl acrylate (all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate, isobornyl methacrylate, acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile, Styrene, functional methacrylate, propionate, and styrene [selected from methyl propionate glycidyl ester, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutyl methacrylate (all isomers), methyl methacrylate, α-hydroxymethyl acrylate Ethyl acetate, α-hydroxymethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, triethylene glycol acrylate , Methylene succinic anhydride, Methylene succinic acid, Glycidyl acrylate, 2-Ethyl acrylate, Propyl acrylate (all isomers), Butyl acrylate (all isomers 20-paper) Standards are applicable to China National Standard (CNS) A4 specifications (21G χ 297 issued) —t -------- installation -------- order --------- (Please read first Note on the back, please fill in this page again) 558558 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 Β7 18-V. Description of the invention () Body), N, N_dimethylaminoethyl acrylate, N, N acrylate _Diethylaminoethyl acetate, triethylene glycol propionate, methacrylamide, N_methacrylamide, N, N_dimethylacrylamide, third butylmethacrylamine Amine, N-n-butyl methacrylamide, N-hydroxymethyl methacrylamide, N-hydroxyethyl methacrylamide, N-tert-butylpropionamine, N-n-butylpropene Ammonium amine, N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, vinylbenzoic acid (all isomers), diethylaminostyrene (all isomers), methylvinylbenzene Osmic acid (all isomers), diethylaminomethylstyrene (all isomers), p-vinylbenzenesulfonic acid, p-ethylfluorenylbenzenesulfonic acid sodium salt, trimethoxysilyl methacrylate Ester, triethoxysilyl methacrylate, tributoxysilyl methacrylate, diethoxymethyl silyl methacrylate, diethoxymethyl methacrylate Methylsilyl propyl, dibutoxymethylsilyl methacrylate, diisopropoxymethylpropyl propylpropionate, dimethoxysilyl propyl methacrylate, methyl Diethoxysilyl acrylate, dibutoxysilyl methacrylate, diisopropylsilyl propylpropionate, trimethoxysilyl acrylate, acrylic acid Triethoxysilyl propyl, tributoxysilyl acrylate, dimethoxymethylsilyl acrylate, diethoxymethylsilyl acrylate, dibutoxymethyl acrylate Silyl propyl, diisopropyloxypropyl propyl acrylate, dimethoxypropyl propyl acrylate, diethoxy propyl acrylate, dibutyloxy propyl acrylate , Diisopropoxysilyl acrylate, vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleic anhydride, N-phenylmaleimide, Ν-Butylmaleimide, Ν-Vinylpyrrolidone, Ν-Acetyl-21-This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) l · (Please read first (Notes on the back then fill out this page)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 558558, Invention Description (Jiyin Jun, Ding Di Association, 2-methyldeca 3-butane, 2-Gas), 3-butadiene, ethylene, and propylene. &Quot; b Applicable monomers include copolymerizable monomers such as those disclosed in the International Patent Application] Said and Solerman, "Free radical polymerization chemistry," Pagman, London, 1995, p. 162.171, and German and Solerman free radical chemistry, Pagman, London, 1995, page 17 and 186 are described as ring-opening monomers. The monomers used in the block copolymer should be selected from the U and V segments. In Disperse 4, it is oleophobic or immiscible and has a tendency to aggregate, while other types of shoulder-capable agents are miscible or compatible with the dispersion medium. The monomer can be selected to provide the phase with the encapsulated material. Compatibility, and compatibility with the medium used for the end use. If the polymer and the medium are chemically similar, or if they are formed to cause special interactions (such as hydrogen bonding), the polymer will dissolve in the dispersion medium (usually It is a low molecular weight liquid). It can also be enhanced by changing the temperature or pH of the dispersion Reduce the solubility. The inventors of Yamamoto found that the "solubility parameter" provides a useful guide to the extent to which the solvotropic block in the block copolymer dissolves in the dispersion medium. The solvotropic property is related to the low solubility parameter. Conversely, it has Relatively high solubility parameter bodies produce relatively insoluble solvent-repellent blocks. It was found that by using the solubility parameters of the solvent-repellent blocks in the block copolymer, the formulator can choose the monomer that provides the micelles. Therefore, By selecting a monomer mixture with a lower solubility parameter to lower the solubility parameter of the lyotropic block, the solvolytic ability of the obtained lyotropic block can be reduced. Therefore, the formulator can obtain a suitable 22- Standard (CNS) A4 specification (21〇X 297 mm) —.------- JAW— I -------- ^ --------- (Please read the Note: Please fill in this page again.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 558558 A7 ___ B7_ V. Description of the invention () The best solvent-solvent / solvophilic block balance for a variety of microgel applications, such as encapsulation Apply or improve a molded tree Impact strength. The solubility parameters of monomers and polymers are known and can be obtained from a variety of sources, such as from E. Grulke, Polymer Handbook, Third Edition (1989) ", Solubility parameter 値" [J. Brandup and E. · Immergut editor (publisher: New York, John Wiley and Sans) (John Wiley & Sons, New York, New York)], or by Allan FM Barton, Handbook of Polymer-Liquid Interaction Parameters and Solubility Parameters, 1990 edition [Publisher-Flory Tak, Pocariten, CRC Press (CRC Press, Boca Raton, Florida)]. Homopolymer-soluble or miscible hydrophilic monomers include monomers used to produce the polymers mentioned in WIPO Patent No. 97/49387, pages 21-25, and should be familiar with the art People understand. Homopolymer-soluble or miscible oleophobic monomers include monomers used to produce the polymers mentioned in WIPO Patent No. 97/49387, pages 3 1-63, and should be familiar with this. Artists understand. One advantage of RAFT polymerization is that a wide range of monomers can be tolerated. It should be noted that a proportion of the solvophilic monomer can be included in or opposite to the oleophobic block without breaking the overall solvophilic-solvotropic balance (it may be necessary to combine cross-linking functional groups or provide For compatibility of encapsulated materials). The dispersion medium may be organic or aqueous, or an aqueous solution containing a co-solvent, such as an alcohol. The medium should be selected to ensure that the oleophobic blocks of the block copolymer are insoluble and the solvent-soluble blocks are soluble. Depending on the nature of the block copolymer, it may need to be different. -23- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 issued)-~ __ i I an I n II Hi II —ϋ n ϋ in ϋ I nnm ί I in ϋ (Please read the notes on the back before filling this page)

558558 V. Description of the invention ()> Cereal mixture. Preferred agents include aromatic hydrocarbons such as toluene, solvesol 100, paraffin oil or mono-toluene 'nitro tiger' such as i-nitropropane and 2-nitropropane; ketones such as fluorenone · pentyl ketone, fluorenyl • isobutyl ketone, methyl • ethyl ketone or acetone; 酉, such as butyl acetate or hexyl acetate; glycol ether esters, such as propylene glycol acetate monomethyl ether. When the dispersion medium is predominantly water, the medium often contains one or more solvents' which may be water-soluble or water-reducing solvents or mixtures thereof. Some suitable solvents include (^ to. ^ Mono- and di-alcohols, such as isopropanol, ethanol, methanol, butanol, 2-ethylhexanol, and dodecanol. Tetrahydrofuran, (ethyl) glycol ethers, and acetic acid (ethyl ) Glycol ester ethers are also suitable. Other solvents include methylbenzyl, hexamethylene, butyl cello solve, butyl cellosolve, carbitol. Some solvents are from Missouri, Midland, Dow Chemical The company obtained (Dow Chemical Company, Midland, Michigan), such as propylene glycol monomethyl ether, ethylene glycol acetate hexyl ether, ethylene glycol n-butyl ether, dipropylene glycol and acetate ether. Preferred is isopropyl alcohol and ethyl ether. • Ethyl ketones and acetone. HAPs solvents such as ethanol, butanol, butyl acetate, isobutanol, acetone, diacetone alcohol, methyl groups are also suitable if needed and to reduce HAPs (harmful atmospheric pollutants) • Methyl amyl alcohol, cyclohexanone, first amyl acetate, methyl • amyl ketone, 2-ethylhexanol, propanol, ethyl acetate, tetrahydrofuran, isopropyl acetate, acetic acid 2- Ethylhexanoate, ethyl ethoxypropionate, amyl propionate Purpose, ethanol, n-butyl propionate, tertiary butanol, and 1-pentanol. -24- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --- 1 ---- --- AW.—Equipment -------- Order --------- AW1 (Please read the precautions on the back before filling out this page) Printed by the Employee Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 558558 A7 V. Description of Invention (The macromonomer of Formula IV includes those disclosed in International Patent Application No. WO96 / 15157 and U.S. Patent No. 5,264,530, the disclosures of which are incorporated herein by reference. It also discloses that they can be activated during manufacture. The reaction conditions for these compounds in prepolymers. The macromonomer preferably contains up to two double bonds, and more preferably contains double bonds. ° This type of macromonomer can be prepared by several different methods. Two descriptions The preparation method is: (1) using a catalytic chain transfer agent containing co (II) or conin; (2) using an addition-cracking transfer agent. These methods are made by Rizzard〇 et al. In Macromol. Symp. 1997, 111, 1. Block copolymers with thiocarbonylthio groups can be found in International Patent Publications WO98 / 01478, WO 99/05099 and WO 99 / 31144 is prepared by the method described herein, and each patent is incorporated herein by reference. These publications specifically disclose thiocarbonylthio compound bond transfer agents and reaction conditions using these compounds. When the incompatibility in the latter stage results in micelles When acting, the block copolymers of the present invention may undergo self-combination (or micellar effect), or be produced by known methods. These include dispersing the block copolymer in a block insoluble solvent; changing the pH of the solution , Such as ionizing a block. Preferred oleophilic blocks contain oleophilic monomers, such as those with hydroxyl functional groups, acid functional groups (such as leptate, continuous acid, osmic acid, and / or phosphonic acid substituents) or quaternizable nitrogen (such as pyridine, primary , Secondary or tertiary amine substituents). The lyophilic hindrance can also be constructed by polymer terminal functionalities, such as polyethylene oxide or polylactic acid. Preferred solvotropic blocks contain solvolytic residues, such as polymerized styrene, (meth) propanoic acid, acetic acid esters, and amidines. Can also be used by the terminal function -25- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Read the note on the back and fill in this page Printed by the Employee Consumption Cooperative 558558 A7 ---- ^ ____ B7___ V. Description of the Invention (23) Function to build a solvophilic block. Preferred reactive monomers suitable for cross-linking reactions include reactive double bonds [e.g., 'allyl (meth) acrylate, cinnamo (methenyl) acrylate], epoxy (e.g. glycidyl (meth) acrylate) Esters), isocyanates or anhydrides (such as maleic acid). Cross-linking reactions are also suitable for monomers containing other functional groups, including carboxylic acids (such as methacrylic acid), hydroxyl groups (such as hydroxyethyl methacrylate), and secondary amino groups (such as dimethylaminoethyl methacrylate) ), Pyridine (acid) groups (such as vinylpyridine), carbamates or ureas (for cross-linking with melamine (melamine) street bio) and similar functional groups. The micelles produced according to the present invention can be stabilized by cross-linking in the shell, core or both '. To this end, cross-linking agents can be added or reactive functional groups can be activated, irradiated or heated. The concentration of micelles is preferably selected to limit the inter-micellar reactions that can cause macroscopic gel formation. These are particularly important when constructing cross-shell crosslinked micelles. Various methods for forming cross-linked micelles are described in the art [eg, Wooley et al., WIPO Patent No. 97/49387], using the information provided, those skilled in the art should know So far, these and other methods can be applied in combination with the present invention. For example, a free radical initiator and an optional polymerizable monomer may be added to a solution including a micellized block copolymer containing a pendent double bond, and then the solution may be heated or irradiated to decompose the free radical initiator. Initiators and monomers are generally selected for their solubility in the polymerized segment containing reactive functional groups. As an example of further crosslinking, a diol or a diamine may be added to a solution containing a micellized block copolymer containing a pendant isocyanate group. The number of side groups and the concentration of added reactants determine the crosslinking density, and therefore the microgel particle -26- ^ Paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) III n ϋ ϋ n I ϋ I n I l II ϋ I -0-0, · ϋ ϋ ^ 1 ^ — ϋ I (Please read the precautions on the back before filling out this page) 558558 A7 V. Description of the invention (24 Permeation through the cross-linked domain) The structure of the preferred block copolymers used in the present invention is shown by Formula V-VIII, and each formula is derived from Formula I-IV, respectively.

S-u-v-R

V

-V-R ·

s—V 一 υ—R

Va • V—U-—R. S ·

R—V * · —U—S h2c: -Z '

VI, CH2-u-v-p

X

VIII • R—U—v—S Via Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs z

Vila H2C '

ch2 ~ v_U_PX Villa It should be noted that the group z can also be -SR, at this time the block copolymer has the formula -27. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇X 297 Mm) (Please read the notes on the back before filling out this page)

25558558 V. Description of the Invention (Structure of IX or X S: S = c

SVU * · —R Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs IX Among them, R, R ^, Z, Z; i, P, U meaning; and each of R can be the same or different t to form a list of U and V A detailed example discloses WIPO Patent No. 97/49387, which is incorporated herein by reference. The crosslinkable group present in the crosslinkable block copolymer of the present invention may be present in the groups R, R !, Z, Zl, P or x, and may be incorporated into the base solid U or V by polymerization. Reactive monomer. X, P, R and Z are groups derived from a RAFT agent of the formula I_ιν. The polymeric blocks U and V may themselves be block or random copolymers. For example, a preferred block copolymer has such a structure, where U is poly (butyl methacrylate-co-methyl propionate) -poly (butyl methacrylate) And V is poly (methacrylic acid). In the block copolymer described above, the block U is a more solvophobic block, and the block V is a more hydrophilic block. Block U contains a functional group (allyl) capable of polymerizing a cross-linking radical. '· Another preferred structure is where U is poly (hydroxyethyl methacrylate ... methacrylic acid is more than 2-ethylhexyl_co-isobutyl methacrylate), and V is

XV, X and n are installed together as stated above -------- Order --------- AWI. (Please read the notes on the back before filling this page) -28- 1 x 297 mm) A7 '~ -------— B7 Ding 20 | ........ 11 V. Description of the invention () (Acrylic acid-co-methyl methacrylate · co-acrylic acid forma Ester-co-phenylethyl ethoxylate).

In the block copolymers described above, block U is a more solvophilic block, and block V is a more sparse solvent that also contains functional groups (acid groups) that can be cross-linked with, for example, diepoxides or diamines. Sexual block. And another preferred structure is that u is ethyl methacrylate_co-ethylhexyl methacrylate-co-isobutyl methacrylate) and V is poly (glycidyl methacrylate-co -Methyl methacrylate-co-methyl acrylate · co-styrene). At this time, block U is a more solvophilic block, and block V is a more solvophobic block that also contains a functional (epoxy unit) capable of being linked to, for example, a dibasic acid fork. The total molecular weight of the block copolymer of the present invention is specified in terms of block length, and is expressed as a number average degree of polymerization ', and is not expressed by a weight average molecular weight. The degree of block polymerization is defined as the number of monomer repeat units in a block. The block copolymer of the present invention has a preferred block length of 5 to 1,000, more preferably 5 to 100, and most preferably 5 to 50. The polydispersity is the ratio of the weight-average polymerization degree to the number-average polymer. The block copolymer of the present invention preferably has a polydispersity of less than 2.5, more preferably less than 8, and more preferably less than 1.4. _ The ratio of the two blocks of the diblock copolymer is preferably 1:20 to 20: 1, more preferably 1:10 to 10: 1, and most preferably 1.5 to 5: 1. The molecular weight and composition of the block copolymer are selected to take into account specific monomer properties, the desired micelle structure, and the intended use of the microgel. -29- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297) (Please read the precautions on the back before filling out this page) Packing > σ. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 558558 A7 B7 V. Description of the invention (In the general method of preparing uniform particle size micelles, the above-prepared block copolymer is dispersed in a medium to dissolve (miscible) one of the block components, while other types are not easy Dissolved or insoluble (immiscible). The homopolymerization can be used to help the block copolymer to disperse by ultrasonication or heating. Soluble block components form micellar shells, while insoluble or insoluble block components form micelles. Core. The concentration of the block copolymer should be selected to be greater than the critical micelle concentration and low enough to form a dispersed micelle of the desired size. This concentration depends on the critical micelle concentration of the block copolymer. It is generally 0.001% by weight In the range of 70% by weight, more preferably in the range of 0.1% to 10% by weight. However, it should be noted that when the particle size polydispersity is not critical, it is best to use it for environmental and economic reasons. Large solid content. For example, poly (fluorenyl butyl acrylate) · insert-poly (methacrylic acid) (a solvotropic-solvophilic block copolymer) can be dispersed in water or a solvophilic solvent 'to form Wherein the fluorenyl acrylic acid segment forms a shell and the methacrylic acid f-butyl ester forms a micelle core. The same block copolymer can be dispersed in a hydrocarbon solvent to form a core in which the methacrylic acid segment forms a core. Opposite micelles. To generate micellar effect, it is also possible to take a solution in which a block copolymer is dissolved in a mutual solvent, and then disperse the solution in a block insolvent, thus changing the ratio of the drop agent to the insolvent. Design a single-pot process for synthesizing block copolymers and generating micelles. Therefore, another embodiment of the present invention provides a method for manufacturing these microgels, which includes the following steps: Provide one or more of the above 4 pages And the solution of cross-linkable block copolymer described on page 5; -30- Μ Zhang scale is applicable to China National Standard (CNS) A4 specifications ⑵Qχ tear public hair (please read the precautions on the back before filling this page) Binding: Ministry of Economic Affairs Hui Property Office employees consumer cooperatives printed 558,558

5. Description of the invention () The solution is dispersed in a solvent-free block of a copolymer to form micelles, and the micelles are crosslinked to form microgels. The invention may further include: A. Encapsulating a second group of molecules or particles in polymer particles produced by micelle cross-linking, and / or B. Preparing microcoagulation that can be modified by making the arm chain grow Micelles or crosslinked micelles. The second group of molecules includes molecules that are difficult to dissolve or disperse on other occasions, such as dye molecules, organic and inorganic pigments, catalysts, and aluminum powder. It also includes pharmaceuticals, medicines and other biologically active molecules. When considering encapsulation of molecules or particles of a third group (point A above), the following preferred specific examples of the above method can be used in whole or in part ... (I) (i) The fluorene copolymer can be dispersed in the medium To micelle the block copolymer (to generate a crosslinkable micelle). (Ii) The solution to be encapsulated is then added to the solution. The material is preferably partially soluble in the solvent medium but highly soluble in the micelles to migrate into the micelles through the solvent medium. (I i i) The micelles are then crosslinked. ϋ 1_1 nn ϋ n amm— nn ft— I mn I Γ Qing Please read the notes on the back before filling out this page} 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (II) (i) Plastic materials can be coated A solvent medium is added, at which point a partially decomposed suspension is formed. (I i) A block copolymer that can be dispersed in the medium can be added (where the block copolymer is micellized to form a crosslinkable micelle). The encapsulated material is moved into the micelles through the mixture. (Iii) The micelles are then crosslinked. (III) (i) The Xin segment copolymer can be dispersed in a medium, where the other segment of the copolymer is micellized (to form a crosslinkable micelle). (H) The micelles are then crosslinked. -31-This paper size applies to China National Standard (CNS) A4 (210 X 297 Public Love) 558558 A7

V. Description of the invention () Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (iii) Then immerse the crosslinked micelles in the solution containing the material to be encapsulated. Encapsulated materials are more soluble in crosslinked micelles than in solution, so they migrate into micelles. (Iv) separating micelles containing encapsulated material from the solution. Regarding the preparation of post-preparation microgels or crosslinked micelles that can be modified by growing arm chains, the following modification steps can be fully or partially used: Microgels can be prepared according to the method of the present invention, followed by the addition of monomers And initiator. Polymerization 'to extend the arm chain of the block copolymer. This process also forms part of the invention. The products of the above processes therefore include: (a) an uncrosslinked mid-block copolymer micelle dispersion, (b) a micelle with a crosslinked shell, (c) a micelle with a crosslinked core, (d) Micelles with both crosslinked shells and crosslinked cores, (e) Crosslinked micelles that react afterwards. Although the microgels formed by the present invention are sometimes spherical, they can also have more complex shapes or structures, depending on the nature of the block copolymer, the combination conditions, and the end use. The microgels of the present invention can take various shapes and forms. The shape may include a sphere, a disk, a needle, a cone, an ellipsoid, a vesicle, a drop sphere, or any other shape formed by a properly constructed block copolymer itself. The particles can be in the form of core / shell and core / shell. Core / shell particles with incompletely encapsulated cores, core / shell particles with multiple cores, and interpenetrating network particles are also included. In either case, the majority of the surface of the particle should be occupied by at least one external phase, while the interior of the polymer particle is occupied by at least one internal phase. The ideal form is selected according to the application -32- This paper size is applicable to the Chinese National Standard (CNS) A4 (21〇χ 297 mm) (Please read the precautions on the back before filling this page) ^ n I * ϋ ϋ n · ϋ ϋ ϋ * ΜΗ · ΙΜΒ Ι · w W · Printed 5 places 58 A7 by the Consumer Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs " " " '--------— B7___ —___ V. Description of the invention (30 ), And is controlled by selecting the block copolymer composition, concentration, dispersion medium, and other process conditions (such as temperature, pH, and ionic strength). Microgels can also be used to improve ease of handling by acting as a lubricant or rheology modifier. They improve the structural strength and dimensional stability of products such as coating compositions and molding resins. When used as a toughener or additive for high impact polymer resins, microgels are generally prepared with low% block crosslinked cores that eliminate stress in the molded article. Examples of low Tg polymers include acrylates (such as 2-ethylhexyl acrylate), siloxanes, polyalkylene glycols, and polybutadiene. The microgel body should be selected so as to be miscible or compatible with the matrix polymer, and generally have an obstacle length greater than the molecular weight of the entangled matrix polymer. Microgels can be used to encapsulate particles or molecules. It can be used to dissolve or disperse molecules that are difficult to dissolve or disperse on other occasions. For example, the coating composition to which the microgel of the present invention is added may include any conventional pigment generally used in conventional or water-loaded coatings, such as metal oxides, including titanium dioxide, various colors of iron oxide, zinc oxide, etc .; carbon black; Agent pigments, such as talc, pottery clay, barite, carbonates, silicates; various organic dyes, such as quinacddones, phthalocyanines, scandium, azo dyes, indigo _ (indanthrones); Ye Jun (carbazoles), such as Yin Jun purple, isoindolinone, isoindolinone, thioindigoreds and benzimilinone; dye molecules; contact Powders for metal and metallic coatings. Microgels can be used to concentrate various substances from solution, and as chelating agents, they are generally used to remove toxins, concentrate metal ions, or dye molecules (to prevent dye transfer during washing). In this case, a microgel phase was Formed to have an affinity for the species to be integrated, while other microgel phases promote the dispersion of microgels in the eight teachings AW * I ^ ----------------- (Please read the back first (Notes for filling in this page)

558558 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 31-* ~ — V. Description of the invention () Medium to easily separate the microgel containing the chelated material from the dispersion medium. The microgel can also be used as a nanoscale reactor when the microgel-containing reagent is in contact with other reagents added to or present in the dispersion medium. Such applications are best suited for integrated chemistry, sensors, and diagnostics. The shell and core crosslinked micelles of the present invention are very widely used in medical, medical and agrochemical applications. For example, these micelles can be used to control the release of pharmaceuticals, diagnostics, herbicides, pesticides and other biologically active materials, such as Woolley et al., WIPO Patent No. 97/49387 (Shell Crosslinking System ) And Nair disclosed in U.S. Patent No. 5,078,994 (Nuclear Crosslinking System), both of which are incorporated herein by reference. Since the microgels of the present invention can be prepared in a variety of structures or compositions, making them suitable for controlled release applications, the applicability of the foregoing methods can be greatly expanded. The microgels of the present invention are also suitable for a variety of coatings, such as automotive OEM and refinish coatings; industrial coatings, such as coil coatings, wood finishes and floor finishes; printing inks; coatings on solvent-sensitive substrates such as leather; Sealants; overprint varnishes; label varnishes; paper coatings; ceramic adhesives, metal coatings on empty ships, polymeric substrate coatings, traffic and area marking paints, glaze coatings, wall coatings, transparent coatings on sensitive substrates, such as technical targets coating. Other optional ingredients can be ideally added to coating compositions such as antioxidants; flow control agents; rheology control agents such as fumed silica and non-aqueous dispersions (NADs); UV stabilizers; UV shielding, quenchers and absorption Agent. In coating applications, microgels can also be processed to act as rheology modifiers, dispersants, wetting agents, slip agents, scavengers, defoamers, plasticizers, and rots. -34- This paper size applies to China National Standard (CNS) A4 Specification (210 X 297 mm) --------- AW—Installation -------- Order ----- AW1 (Please read the back first Please note this page, please fill in this page) 32558558 Description of the invention (Syringe inhibitor. The invention will now be described by way of example. Shenfu is limited to this by the formula ^ Shi 1-He Shi Shi Wan. The following two examples illustrate the synthesis of solvating solvents. Properties_Solvent-soluble ABC triblock ugly polymer, the copolymer contains methacrylic acid di- and ester units in the lyophobic C block. Example 1 Preparation of Propionate Macropropionate Monomer is filled with 600.5 g of distilled water A 5-necked, 100 ml mechanical stirrer (please read the precautions on the back before filling out this page) "-Install the printed container of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and then blow nitrogen through the solution for 20 minutes Purify while heating the reactor contents to 60 ° C. Start the monomer feed at 2.5 ml / min. Feed: 曱Acrylic acid (inhibited at 150 ppm MEHQ) The cobalt catalyst was added to the reactor at the beginning of the monomer feed. 277 g 3 4 mg Batch 1: Initiator (Wako-VA_044) 1.2 g distilled water 12 g 2 batches: cobalt catalyst [iprCo (III) (dpg-BF2) 2] 30.2 mg of acetone (AR) 5.0 ml After 60 minutes (from the start of monomer feed), the third batch was added. The third batch was initiated Agent · 0.6 g of distilled water 6 g is added to the fourth batch 'to make the mixture replenished at 60 t. After the monomer feed is completed, the reaction is performed for another 60 minutes. The fourth batch of initiator is 0.6 g ---- order — # -35 this paper ; Zhongguanjia Standard (CNS) A4 specifications (210 x 297 mm) 558558 A7 B7 33 V. Description of the invention (

Distilled water 6.U on a rotary evaporator (the room is empty, the macromonomer is separated from the solution on a water bath 8 (rc) to obtain a light brown powder, which is redissolved in distilled water (approximately 25% weight / volume polymer ), And use warm (water bath) to help dissolve. Then use a rotary evaporator to separate the macromonomer product to obtain a light blue_green solid that can be easily ground into a powder. Use a mortar and pestle to grind the macromonomer into The powder was then dried in an air-drying oven overnight (30 mm Hg @ oven temperature 80 ° C). Characteristics: iH-NMR in dms0-d0 showed no residual monomers present. Compared to the overall polymer, 'terminal double bond resonance' The integral indicates that the number average molecular weight is 12,000, which is equivalent to an average of 14 methacrylic units per macromonomer chain. Preparation of poly (fluorenylpropanoic acid) _post_poly (butyl methylpropionate) _embedded _Poly (Methyl Propionate-Co-Methyl Propionate) Purpose: A 3-necked, 250-milliliter reactor was assembled with a magnetic stirrer, condenser, and gas purifier, and 40.34 g of AR isocyanate was added. Propanol and 1.04 g of methacrylic acid macromonomer. The reactor contents were heated to reflux (80 ° C), dissolving the macromonomer, and then purging nitrogen through the solution for 20 minutes to purify. Initial filler: 100 g of methacrylic monomer, 40.3 g of isopropanol, start monomer feeding at 0.06 ml / min, Feed for 15 minutes. Feed 1: n-butyl methacrylate @ 8.05 g at the beginning of the monomer feed. Add the following batch to the reactor. 36- This paper size applies the Chinese National Standard (CNS) A4 specification (2 〖〇X 297 public love） * Outfit -------- Order --------- (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 558558 Α7 Β7 V. Description of the invention (34 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the first batch: Initiator [Azobis (isobutyronitrile)] Propidium is fed after 150 minutes (from the start of monomer feeding) Material 2: n-butyl acrylate, n-butyl acrylate, allyl acrylate is intended to start the monomer feed, the following batch is added to the reactor batch 2: initiator [azobis (isobutyronitrile)] acetone. After 1 minute for 90 minutes (from the start of the second monomer feed), add a third 8 g of this mixture and heat at 80 ° C. 90 minutes batch 3: Initiator [azobis (isobutyronitrile)] 0 g acetone '0.9 g total reaction time was 330 minutes. The reaction mixture was cooled to room temperature. Isolation: On a rotary evaporator (The chamber was emptied, and the block copolymer was separated from the solution with a water bath 8 (rc) to obtain a white powder. It was redissolved in isopropanol (about 25% weight / volume polymer) with warming solubilization. Rotate again The unsubstituted or substituted product was separated by an evaporator to obtain a primary solid which was easily ground into a powder. The # segment copolymer was ground into a powder with a mortar and pestle, and then dried in an air-drying oven overnight (30 mm Hg). @ Oven temperature 80 ° C). Gel permeation chromatography of the copolymer showed a peak molecular weight (Mp) of 2405 g / mole. 1 H NMR proved to be consistent with this osmium. Add feed 2. 0 · 21 grams 143 grams 4, 1 grams 40 grams and will (please read the precautions on the back before filling this page) Binding ---- Order ------ -37- This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) 558558 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 35 V. Description of the invention () Conversion rate of monomer-forming polymer> 90%. The following examples illustrate the use in Solvent-solubilizing C-solvent-solvent-solvophilic ABC triblock copolymer containing allyl methacrylate, and forming nuclear cross-linked micelles to encapsulate the dye. Example 2 Poly (fluorenyl propionate) Pyranoic acid) -fluorene-poly (fluorenylpropionate @ butyl) _Inlay-poly (methyl methacrylate, acrylic acid-co-butyl methylpropionate) to form nuclear cross-linked micelles containing dyes Poly (methacrylic acid) -inserted-poly (butyl methopropionate) prepared in Example 1 · Methyl-poly (allyl methacrylate-co-butyl methacrylate) (MAA -ΒΜΑ-ΑΜΑ) (0.1 g) was dissolved in methanol (30 ml). Water (70 ml) was added with stirring. A slightly mixed blue solution was obtained. To determine the nature of the solution, 芘 (0. 0. 4 g [Langmuir 1990, 6, 514-516] was added as a fluorescent detector, and the mixture was stirred for 15 minutes to equilibrate. 芘 is an organic dye 'and poorly soluble in water. In 70:30 water-methanol In the mixture, 芘 is at 330.0 nanometers (λ em396 nanometers (showing the fluorescence excitation spectrum with (0, 〇) band. In the above micellar solution, the same band was transferred to 332 6 nanometers, indicating that You are not in the open solution. 芘The cast film of MAA-BMA-ΑΜΑ shows that the band is at 332.6 nanometers. Therefore, the solution of the copolymer contains micelles in which osmium is added. Particle size experiments determined that the average micelle size was 40 nanometers (9 5 % Distribution: 2 5-6 1 nm). Another way to determine the generation of micelles and display the characteristics of the internal environment of the micelles is to compare the intensity of You 13 and h emission bands (Aus j Chem. 1987, 40, 1). At 70 : In a 30% water-methanol mixture, tritium shows a fluorescence emission spectrum with 1 ^ 1 = 0.73. When the copolymer is present, it changes to l3 / Ii == 1 〇5. The -38- This paper size applies to China National Standard (CNS) A4 Specification (21 × 297 mm) --- 1 ------- I ^ -------- Order ----- ---- (Please read the precautions on the back before filling this page) 558558 A7 V. Description of the invention (> 丨) is a non-polar environmental feature (separate in hexane; separate) In water, ΐ3 / Ιι = 〇.59). Therefore, the micelles surround the relatively non-polar environment where 芘 is present. Then add the mixture to teach $ ^. Initially heated to 50 C, phenylethylhydrazone (2003 g) was added. The mixture was stirred for 1 to 2 hours to achieve a balance of 1,000 lbs., And then polymerized with AIBn (/0.004 g) in an inert atmosphere overnight to form a corresponding core-shell polymer. After cooling to the ambient temperature, the excitation spectrum of the milk mouthpiece showed that the band (0, 0) shifted to 347.0 nm. The results are consistent with the presence of polystyrene in the core of the microgel enclosing each specific molecule. The particle size I test showed that the average particle size was expected to increase to 6 8 nm (95% distribution: 4 3 _ 9 8 Nanometers). ^ Is the stable content of the polarity change, and the stability of the dissociation effect of the polymerized microgel is shown in the following example. The solution containing the above tests to prepare the cross-linked micelles has obvious micro-dispersion, micro-blue characteristics. Adding methanol (30 drops) to the solution (1 ml) has a different appearance. Therefore, when the solvent medium has a very small polarity, the microgel persists and the solution of the non-parent micelles (that is, In comparison with nuclear cross-linked microgels, when the control experiment was performed, the solution became clear and lost the fuzzy blue color when treated with methanol under the same conditions. It indicates that when the medium has less polarity, the unlinked micelles dissociate. Therefore, the crosslinking process stabilizes the micelles. Example 3 The poly (methacrylic acid) · insert-poly (butyl methacrylate) -poly (allyl methacrylate_co-butyl methacrylate) prepared in Example 1 (0.5 g) / Grain isopropyl alcohol (5 ml), add the mixture dropwise to turbulent water (150 * liters) at 95 ° C. Stir the resulting solution at this temperature for 30 minutes, during which alcohol is distilled -39- this paper size Applicable to China National Standard (CNS) A4 specification (21 × 297 mm) (Please read the precautions on the back before filling out this page) Packing: Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 558558 A7 37 V. Invention Description (Hair. After cooling to 80 ° C, 0.2 g of dye was added. We found that within 4 hours the dye was extracted and dispersed into the micellar solvent core generated by the copolymer. The crosslinking reaction started at this stage. Pass the above The mixture was blown with nitrogen bubbles, and the nitrogen atmosphere was maintained above, thereby thoroughly degassing the mixture. After degassing and stirring for 3 hours, the temperature of the above mixture was maintained at 800 c, and a radical initiator azobis ( Isobutyronitrile) (AIBN) (20 mg). With vigorous stirring Add methyl methacrylate (0 · 丨 g) at 0.0017 g / min (completely added after 1 hour). Continue polymerization for an additional 3 hours. Then test the encapsulated dye: known mixture (hereinafter referred to as mixture A). In order to assess the degree of dissolution and dispersion of dyes in micelles or cells produced from block copolymers, solvation coloration or related physical characteristics can be used to test the physical environment changes of dyes (for example, transfer to High or low energy absorption spectrum, relative intensity change of different absorption / emission bands or fluorescence decay period). = The dye used in the example shows that the fluorescence half decay time (FDH) is a highly environmental feature. In a pure solid state, the FDHMm time of the dye Units. When dyes are put into highly dispersed, polymer films, higher yields are obtained (3.0-4.3 time units in polystyrene films, 4.3 in polymethylpropionate films) 1 time unit). When dissolved in a solvent under air, due to the presence of oxygen in the solution, a very short FDH was observed (0 2 _ 0 3 time units in xylene). The FDH of the dye in Mixture A was 3 · 7_38 time unit, indicating a high degree of dispersion, the results obtained by the cast polymer film ㈣. After 24 hours of monitoring time, the 値 is stable. In order to test the stability of nuclear crosslinked micelles, a large amount of broken chain acid salts Solid-40 This paper is in accordance with Chinese National Standards (CNS) ^ fi ^ (210 χ 297 mm page 558558) Printed by A5 B7, Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, A7 B7 Invention Description (Added to Mixture A. Aluminosilicate Salt solids are generally unstable and destroy the micelles generated by the solvotropic-solvophilic block copolymer. The FDH of the dye in the polymer remains unchanged, but it slowly stabilizes at 24-3 over a period of several hours. Time monomer. This means that the micelles maintain great integrity and are generally unaffected by broken acid solids, although some micelles do become unstable. The following examples illustrate the use of uncrosslinked micelles in the presence of aluminosilicate solids and their lack of stability. Comparative Example In this example, one of the following block copolymers was used: 1. (PMA) 860 inlay- (PBuMA) 1422 2. (PBuMA) u-inlay- (PAA) u 3. (PEG) 750-inlay- (PStykooo 4. (PEG) 750-benzyl- (PBzMA) 10,000 where the general formula (block 1) mWl_block · (block 2) mw2 refers to consisting of two blocks (block 1 and block 2) Diblock copolymer, the diblocks have average molecular weights mwl and mw2, respectively, and the subscript u refers to the segment with unknown average molecular weight. And here PAA refers to the block composed of polyacrylic acid (solvophilic), pBuMA refers to a block composed of poly (butyl methacrylate) (solvotropic), PBzMA refers to a block composed of poly (methyl methacrylate) (solvotropic), PEG refers to a block composed of poly (ethylene Alcohol) (solvophilic) block, PMAA refers to a block composed of poly (methacrylic acid) (solvophilic), PSty refers to a waste segment composed of polystyrene (solvotropic). The segment copolymer is partially soluble in commercially available non-polar solvents, Isopar -41. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm).! * --------- Packing --- ----- Order --------- (Please read the notes on the back before filling this page) 558558

Description of the invention (M. When the polymer is "any" or "0" grams, a suspension is formed. The suspension is mainly composed of a solid and a small amount of a dissolved copolymer; ) Fluorine-based, solvent-based L-Lin salt. The salt used is completely insoluble in Isopar Μ: in a single Tc ^ Λ. _ Muscle

Par Μ heart floatation showed a fluorescence decay half-life (FDL) of 20 microseconds, protecting π: Liang Xi m _ Ma ν) is absolutely characteristic of horse child solid salt particles. However, in the presence of a block copolymer, we found that the salt of the salt gradually increased to 3.G_3.7 microseconds after M hours, and then remained unchanged after the monitoring time. These numbers were also obtained when the salt was dispersed in the above polymer # 膜内 #. Therefore, the solute block copolymer forms micelles, dispersing the amphiphilic dye into its core. Add powdered aluminosilicate solids to the above mixture, and immediately reduce the fdl of the salt to 1.9 to 2.3 microseconds, which is a characteristic of granular solid salts. As a result, the dye becomes solubilized and dedispersed; the presence of polar solids leads to the release of the self-solvent core, which must destabilize the micelles of the solute block copolymer. The following examples (4-6) relate to synthesizing microgels with nuclear crosslinked micelles or micelle aggregates for use as dispersants or rheology control agents in coating formulations. The following example illustrates the use of cumyl dithiobenzoate as a RAFT agent to synthesize terpolymers for use as the "arm" component of a microgel. Example 4 The "arm" component of the diblock copolymer is composed of an acrylate copolymer and is based on the following 5: 4: 1 mass ratio: 2-ethylhexyl methopropionate (EHMA ), Isobutyl methacrylate (IBMA) and 2-hydroxyethyl methacrylate (HEMA). 42 This paper size applies to China National Standard (CNS) A4 (2) 0X 297 public love (Please read the notes on the back before filling out this page) Binding —— Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 558558 A7 B7 V. Description of the invention (4Q) 2-ethylhexyl methacrylate (1000 g), isobutyl methacrylate (800 g), hydroxyethyl methacrylate (200 g), two The reactor was filled with cumyl thiobenzoate (56 g) and toluene (700 g), sparged with nitrogen for 40 minutes, and then refluxed. Then, 28 grams of Vazo (trademark) 88 initiator [supplied by DuPont Company, Wilmington, Delaware, Delaware] was dissolved in 200 grams of toluene and fed over 240 minutes, And kept at reflux for 2 hours. The conversion was determined by the gravimetric method, and the molecular weight was determined by the GPC method (0 / 〇 conversion = 86%, Mn = 8,510, Mw / Mn = 1.95). * The following examples synthesize and combine block copolymers, and then use a double epoxide (Araldite CY-184) and a Lewis acid catalyst (CP66) through the presence of acid groups in the core (accounting for copolymerization Monomer 9% by weight) is crosslinked. The chemical name CP66 is a 2-butenyltetramethylene-hexafluoroanthionate salt. Example 5 (Please read the precautions on the back before filling this page) 〇

〇 CY184 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs will contain an "arm" component (example 4,272 < grams, 70% solids), acrylic acid (28 grams, 9% by weight of "nuclear" monomers) Methyl acrylate (140 g), methyl acrylate (88 g), styrene (50 g), heptane (242 g), and mineral oil -43-, this paper size applies Chinese National Standard (CNS) A4 specifications ( 210 X 297 mm) 558558 Α7 _____B7 _ 41 V. The flask of mineral spirit (65 g) was heated to reflux. 8 grams of vazo (trademark) 6 7 initiator (provided by Wilmington, Delaware, DuPont) was dissolved in mineral oil (93 grams) and butanol (17 grams) and fed over 244 minutes. Micelle generation began within 30 minutes. The conversion rate was 93%. Mn 16,000. Mw / Mn = 2.90. 0.5 mole equivalents of CY184 (based on acrylic acid) and 0.5% by weight of 0.66 (based on total solids) were added to an aliquot of the mixture. The mixture was gently heated under reflux, and the X-linked process was followed by acid rhenium (initial acid 値 = 3 1). After 4 hours (acid hydrazone = 14), add another CY184 / CP66 aliquot. Continue heating for 17 hours (total 21 hours) (acid 値 = 2). Particle formation (X-linked micelles) is clearly visible (insoluble). The reaction yield (or process efficiency) is measured by determining% solubles (unlinked polymer). This includes dissolving a known amount of the reaction mixture into THF. After centrifugation, the supernatant was separated, and the solvent was distilled off to obtain% solubles. In this experiment,% solubles = 35%. The microgel yield was 61% by weight. The following examples illustrate the use of epoxy monomers (glycidyl methacrylate) and cross-linking with polycarboxylic acids (trimellitic anhydride (TMA)). Example 6 ο

〇ΤΜΑ will contain the "arm" component (Example 4,400 g, 70% solids), fluorene-based acrylic acid-44 paper size Gu Zhongjiao Jia Xian (CNS) A4 specification (21U x 297 mm) (Please read first Note on the back, please fill in this page) Installed by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives of the Ministry of Economic Affairs 558558 A7 B7 42 5. Description of the invention () (Please read the notes on the back before filling this page) Glycidyl ester (3 3g 7% by weight of copolymer monomer), methyl methacrylate (233 g), methyl acrylate (139 g), styrene (74 g), heptane (356 g) and mineral oil (96 g) The flask was heated at reflux. 8 grams of Vazo (trademark) 65 L initiator (12 grams) (supplied by DuPont, Wilmington, Delaware) were dissolved in mineral oil (100 grams) and allowed to feed over 6 hours. A precipitate started to form within 30 minutes. Conversion rate> 95%. Mu 17,500. Mw / Mii = 2.60. Gelation was observed at higher GM A content (14% by weight). 0.33 Molar equivalent of TMA (based on glycidyl methacrylate) was added to an aliquot of the mixture. The mixture was gently heated to reflux. Reflux was continued for 29 hours, after which the mixture was analyzed for% solubles. In this experiment,% solubles = 39%. The yield of the microgel is 61% by weight. Example 7 A transparent coating composition was prepared by mixing the following components together, where all parts are parts by weight: Cymel (trademark) 1168 (fluorinated with a degree of polymerization of 1.75) And isobutylated melamine formic acid resin) 122.0 parts of Tinuvin (trademark) 900 solution (30% benzotriazole UV light stabilizer dissolved in xylene) 37.0 parts of Tinuvin (trademark) 079 solution (soluble in xylene 40% solid hindered amine light post-fixing agent) 13 8 parts of crushed oxygen burning solution (70% Dow Corning 62230 with the structural formula shown above, dissolved in solvesso 100 aromatic hydrocarbon solvent, and R is methyl and phenyl) 236.0 parts of propionic acid resin B (prepared below) 162.0 parts Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -45- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 558558 A7 ________B7 43 V. Description of the invention () 217.0 parts of dodecylbenzenesulfonic acid (70%, soluble in isopropanol) of the microgel prepared according to Example 6 9.8 parts of xylene 45.0 parts of butanol 35.0 parts of methanol 13.0 parts Total: 890.6 All clear coating combinations Containing 25% acrylic resin b, 3 0% oxygen broken economic Intellectual Property Office employee consumer cooperative printed burning oligomer, 23% and 22% microgel appearance yl melamine A crosslinked resin passage. The coating composition was adjusted to a viscosity of 28 seconds with diphenylbenzene (as measured with a Ford cup). The viscosity is traded off here at 580/0 (at 60 ° C). A dark blue metallic polyester-modified acrylic melamine primer was sprayed on the electrodeposited steel plate. After 5 minutes, spray the above clear coating composition onto the primer. Two coats are applied to provide a 2 mil clear film. The wet primer / clear coating composition was baked at 130 ° C for 20 minutes. The resulting coating had a high gloss (93 on a 20 ° C gloss meter). Tested with a Tukon Hardness Machine, the hardness is 8 knoop units. The solvent resistance of the coating was shown by the following experiments: 100 round trips with xylene or methyl ethyl ketone without effect; immersion in gasoline over 20 cycles of 5 minutes showed no degradation. The coating has excellent corrosion resistance, as shown in the following experiment: the coated panel was exposed to 10% sulfur on a temperature gradient for 15 minutes, and the surface was not corroded below 55 C; when it was above the above temperature, it was corroded It increases with increasing temperature intensity on the gradient bar. In order to prepare the acrylic resin B, a polymerization of 15% styrene, 300/0 butyl methacrylate, 17% butyl acrylate, and 38% hydroxypropyl acrylate was prepared -46-This paper is applicable to China Standard (CNS) A4 specification (210 X 297 mm) ----------------- Order -------- (Please read the precautions on the back before filling in this Page) 558558 A7 B7 —-~ " 44 V. Description of the invention, and the solid is dissolved in 3/1 Solvesso 100 / dioxobenzene at 70%. At 25 ° C, according to the Garden-Holdt scale, the street fat viscosity was Y-Z1. The weight average molecular weight was 9,800. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 47 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

558558 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs · A method for preparing microgels, comprising: (i) RAFT polymerization of one or more solvotropic monomers and one or more solvophilic monomers in the presence of a seam transfer agent To produce one or more block copolymers, the block copolymer comprising one or more solvophobic blocks and one or more solvophilic blocks, wherein the solvophobic blocks are insoluble in the dispersion medium 'and the The lipophilic block is dissolved in the dispersion medium; (ii) the fluorene copolymer is dispersed in the dispersion medium to form micelles; and (iii) the micelles are stabilized to form the microgel. 2. The method according to item 1 of the scope of the patent application, wherein the solvophobic block &apos;, the solvophilic block, or the two rear blocks has one or more crosslinkable functional groups. 3. The method according to item 2 of the scope of patent application, wherein the crosslinkable functional group is selected from the group consisting of epoxides, renegade systems, derivatives of these systems, liver, light base, isocyanate (salt), allyl , Cinnamon (brew) group, several groups, tertiary amine group, pyridine (acid) group, amino phosphonate, urea and its mixed groups. 4. A method according to item 2 or 3 of the scope of patent application, wherein step (iii) includes cross-linking the cross-linkable functional group. 5. According to the scope of patent application! The method of item, wherein step (iii) comprises growing the copolymer's solvophilic or oleophobic block chain. 6. The method according to item 1 of the scope of patent application, wherein the chain transfer agent is selected from the group consisting of the following: -48- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------- I equipment -------- Order --------- (Please read the note on the back? Matters before filling out this page) 558558 A8 B8 C8 D8 6. Scope of patent application SR Z • R (Π), R-S m Ρ—〇Η &lt; (IV) and the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed their mixtures, where R'R1 and P are free radical degrouping; and wherein R is selected from the following groups Group: unsubstituted or substituted C 1 to C is alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted block, unsubstituted or substituted saturated carbocyclic ring, unsubstituted or substituted Substituted unsaturated ring breaking, unsubstituted or substituted aromatic ring breaking, unsubstituted or substituted saturated heterocyclic ring, unsubstituted or substituted unsaturated heterocyclic ring, unsubstituted or substituted aromatic heterocyclic ring, Unsubstituted or substituted alkylthio and a first polymeric chain having a degree of polymerization from 5 to 10,000; Z is selected from the group consisting of hydrogen, chlorine, unsubstituted or substituted C 1 to C is alkyl, unsubstituted or substituted aryl, unsubstituted or substituted C 3 to C 8 heterocyclic ring, unsubstituted or substituted C 1 to C 8 alkylthio, SR, Unsubstituted or substituted arylthio, unsubstituted or substituted Ci to Ci 8 alkoxy, unsubstituted or substituted aryloxy Base, unsubstituted or substituted amine, unsubstituted or substituted C 1 to c 18 alkane 49- This paper size applies to China National Standard (CNS) A4 (21〇x 297 mm) (Please read the back first (Please note this page before filling out this page) 558558 A8 B8 C8 __ D8 VI. Patent application scope oxycarbonyl, unsubstituted or substituted aryloxycarbonyl, carboxyl, unsubstituted or substituted ci to c 18 methoxy, Substituted or substituted arylfluorenyloxy, unsubstituted or substituted carbamoyl, cyano, C 2 to C 8 dialkylphosphonic acid group, diarylphosphonic acid group, (^ to (: 18 Alkylphosphinic acid group, diarylphosphinic acid group, and a second type of polymer chain having a number average degree of polymerization of 5 to 10,000; R1 is an η-valent moiety derived from R; Z1 is from each of the following groups The η-valent moiety derived from the selected group of groups consisting of unsubstituted or substituted Ci to Ci 8 alkyl, unsubstituted or substituted aryl, and a third polymerization having a number average degree of polymerization of 5 to 1,000 Chain, wherein the linking moiety in the polymer chain is selected from the group consisting of C! To Ci8 aliphatic carbons, aromatic carbons, oxygen, sulfur, and combinations thereof Group; P is an oligomer or polymer having a number average degree of polymerization of 2 to 1000 or the first polymer chain; X is selected from unsubstituted or substituted aryl, Ci to Ci 8 alkoxycarbonyl, unsubstituted A group consisting of substituted or substituted lactoyl, sulphydryl, unsubstituted or substituted aryloxy, Ci to c18 and cyano; η is an integer from 1 to 6; and intellectual property of the Ministry of Economic Affairs Bureau -------------------- (Please read the notes on the back before filling out this page) where R, R 1, Z, Z 1 and X are substituted groups The substituents are independently selected from the group consisting of: hydroxyl, tertiary amine, halogen, cyano, epoxy, carboxylic acid, alkoxy, alkyl having 1 to 32 carbon atoms , Aryl, alkenyl with 2 to 32 carbon atoms, alkynyl with 2 to 32 carbon atoms, saturated carbocyclic ring with 3 to 14 carbon atoms, printed with 3 to consumer cooperatives 50 558558 A8 B8 C8 D8 Sixth, the scope of patent application is unsaturated carbon ring with 14 carbon atoms, aromatic carbon ring with 6 to 14 carbon atoms, saturated heterocyclic ring with 3 to 14 carbon atoms, unsaturated heterocyclic ring with 3 to 14 carbon atoms Rings and aromatic carbon (hetero) rings having 3 to 14 carbon atoms. 7. The method according to item 1 of the scope of patent application, wherein the dispersion medium is a hydrocarbon, and at least 70 mole% of the single system including the solvent-soluble block is selected from the group consisting of isobutyl methacrylate, isobutyl acrylate, Group consisting of 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, isobornyl methacrylate, isobornyl acrylate, and mixtures thereof: at least 70 mol% including lyotropic blocks The single system is selected from the group consisting of phenethylhydrazone, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, hydroxypropyl methacrylate, acrylonitrile, methyl A group consisting of tertiary butylamine ethyl acrylate and mixtures thereof. 8. The method according to item 7 of the scope of patent application, wherein the hydrocarbon includes heptane and mineral spirit. 9. The method according to item 6 of the scope of patent application, wherein the block copolymer has the following structure: * s ^ s—u—V ~ RV g ^ V —-u Han \ z Va (Please read the note on the back first Please fill in this page for further information) «—install tr --------- 0 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs or when the chain transfer agent has the formula I structure, where u is the hydrophobic block , V is the solvophilic block. 51-i Paper Chinese National Standard (CNS) A4 specification (210 X 297 mm) 558558 A8 B8 C8 D8 • Patent application scope 10. The method according to item 6 of the patent application scope, wherein the block copolymer has the following structure : K8 · Nz VII • u- -R or S Ks'Nz Vila • R η When the chain transfer agent has the structure of formula II, where u is the solvophilic block and V is the solvophilic block. I 11. The method according to item 6 of the application, wherein the block copolymer has the following structure: R- • Z η η VI or Via ----------- Installation -------- Order --------- (Please read the notes on the back before filling this page) Ministry of Economy Wisdom When the chain transfer agent has the structure of Formula III, the property bureau employee consumer cooperative prints that u is the solvophilic block and V is the solvophilic block. 12. The method according to item 6 of the scope of patent application, wherein the block copolymer has the following structure: # 52, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 558558 A8 B8 C8 D8 Patent application scope H2C == &lt; ^ CHr X VIII • V · • p H2〇 === ^ or ch: ·· &quot; ·-V * X Villa • u ~ p When the clock transfer agent has the structure IV Where u is the solvophilic block and V is the solvophilic block. 13. According to the method of the patent claim No. 6), the block copolymer in the formula has the following structure: <Su —-V—R This S-JJ-V—R = \ 'S IX S—- V— -U—-R • V-u_R X or printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. When the chain transfer agent has the structure of Formula 1 and Z is _SR, where u is the solvotropic block and V is The lipophilic fungal segment. 14. The method according to item 9, 10, 11, 12, or 13 of the scope of the applied patent, wherein: when U is poly (butyl methacrylate-co-allyl methacrylate wide embedded_poly ( In the case of butyl methacrylate), the V is poly (methacrylic acid); when the υ is poly (hydroxyethyl methacrylate · octaethylhexyl methacrylate-co-isobutyl methacrylate)时 'The V is poly (acrylic-co-fluorenyl-propyl ----------- install -------- order --------- (please read the back first Please pay attention to this page and fill in this page again.) 53- Wheat paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 558558 A8 B8 C8 D8 6. Application scope of patents Methyl acid-co-methyl acrylate-co -Styrene); or when u is poly (hydroxyethyl methacrylate co-2-ethylhexyl methacrylate · co · methyl methacrylate isobutyl vinegar), V is poly (methyl Glycidyl propionate-co-methyl methacrylate-co-methyl acrylate-co-styrene) 15. The method according to item 14 of the scope of patent application, wherein at least one of u or V includes Allyl methacrylate The monomer mixture is produced. 16. The method according to item 14 of the scope of the patent application, wherein at least one of u or V is produced from a monomer mixture containing a glycidyl methacrylate monomer. 17. According to the scope of the patent application The method according to item 4, wherein the solvotropic block comprises a polymerizable group. 18. The method according to item 17 of the scope of patent application, wherein the crosslinking step includes adding a radical initiator and a monomer. 19. According to The method of claim 18 in the scope of the patent application, wherein the polymerizable group is propyl ', and the monomer is methyl propylpropionate or phenylethyl hydrazone. 20. According to the method of scope 5 in the patent application, Wherein the solvophobic block includes a polymerizable group. 21. The method according to item 20 of the scope of patent application, wherein the chain extension step includes adding a radical initiator and a monomer. 22. According to item 21 of the scope of patent application Method, wherein the polymerizable group is allyl, and the monomer is fluorenyl methacrylate or phenethylhydrazone. 23. The method according to item 4 of the scope of patent application, wherein the epoxide consists of the compound (i) Steps to join (A Base) Acrylic glycidol vinegar is produced. 24. The method according to item 4 of the scope of patent application, wherein the (iii) includes the addition of -54- $ paper size applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) ( (Please read the precautions on the back before filling this page) -Install -------- Order ---- # Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 558558 A8 B8 C8 -----__ D8 VI 、 The scope of patent application is 1'2,4-trimellitic acid liver. ^ y • The method according to item 4 of the scope of patent application, wherein when the crosslinkable functional group is a carboxyl functional group, the (iii) includes adding a polyepoxide. 26. The method according to item 25 of the scope of patent application, wherein the carboxyl functional group is generated by adding (fluorenyl) acrylic acid in the step (i). 27. The method according to item i of the patent application, wherein the sparse agent block of the block copolymer has one or more crosslinkable functional groups. 28. The method according to claim 27, wherein the step (iii) includes crosslinking the crosslinkable functional group. 29. The aromatic method according to item 28 of the scope of patent application, wherein the dispersion medium contains 0.1% to 70% by weight of the microgel. 30. The method according to item 1 of the patent application, wherein the oleophilic block of the block copolymer has one or more crosslinkable functional groups. 3 L The method according to item 30 of the scope of patent application, wherein the step (丨 i 丨) includes: crosslinking the crosslinkable functional group. 32. The method according to item 31 of the application, wherein the dispersion medium contains 0.001% to 10% by weight of the microgel. (Please read the note on the back? Matters before filling out this page) I ---- Order --------- ^ 9— Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs , Which contains one or more of the following functional groups: This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 558558 A8 B8 C8 D8, patent application scope S = &lt; s- z • U—V—R · H2C CH2 Ll · —V—-pn XA XIII XIV Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R'R1 and P are free radicals; and wherein R is selected from the group consisting of the following groups : Unsubstituted or substituted C! To C! 8 alkyl, unsubstituted or substituted fluorenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted saturated carbocyclic, unsubstituted or substituted Unsaturated carbocyclic ring, unsubstituted or substituted aromatic carbocyclic ring, unsubstituted or substituted saturated miscellaneous meal, unsubstituted or substituted unsaturated heterocyclic ring, unsubstituted or substituted aromatic heterocyclic ring, unsubstituted Substituted or substituted thiol groups and first polymer chains with a number average degree of polymerization of 5 to 1000; Z is selected from the group consisting of hydrogen, gas, unsubstituted or substituted Ci to Ci8 Alkyl &lt; unsubstituted or substituted aryl, unsubstituted or substituted C 3 to Ci 8 heterocycle,-unsubstituted or substituted ci to ci 8 alkylthio, s R, unsubstituted or Substituted arylthio, unsubstituted or substituted CiSCu alkoxy, unsubstituted or substituted aryloxy, unsubstituted Substituted amino, unsubstituted or substituted C i to ci 8 alkoxycarbonyl, unsubstituted or substituted aryloxycarbonyl, carboxyl, unsubstituted or substituted C 1 to C 8 alkoxy, unsubstituted Substituted or substituted aryl fluorenyloxy, unsubstituted or substituted amine fluorenyl, aryl, C2 to Ci8 dioxanylphosphonic acid group, diarylphosphonic acid group, shanzhi (: 18 dialkyl times Phosphonic acid group, 56 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 cm) * -nn ϋ nn ϋ · ϋ ϋ I «i I nnnnn 一 · ϋ n ϋ I nn · 1 IIII ϋ nt — I (Please read the precautions on the reverse side before filling out this page) 558558 A8 B8 g8s ~ --- --- ______ VI. The scope of patent application for the diarylphosphinic acid group and the second with a degree of polymerization of 5 to 1000 R1 is the η-valent moiety derived from R; (Please read the notes on the back before filling this page) ζ is the η-valent moiety derived from the group selected from the following groups: unsubstituted or Substituted Ci to Ci8 fluorenyl, unsubstituted or substituted aryl, and a third polymeric chain with a number average degree of polymerization of 5 to 1,000 The connecting part in the polymer chain is selected from the group consisting of (: 1 to (:: 18 aliphatic carbon, aromatic carbon, oxygen, sulfur, and a combination thereof); P is a polymer having a number average polymerization degree of 2 to 1,000. Oligomer or polymer or the first polymeric chain; X is selected from the group consisting of: unsubstituted or substituted aryl, (: 1 to 0:18 oxocarbonyl, unsubstituted or substituted aryloxycarbon, Group consisting of aryl, unsubstituted or substituted aryloxycarbonyl, 01 to <318 carboxyl, and cyano; η is an integer from 1 to 6; and the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the R, The substituents of the substituted groups of R1, Z, Z1, and X are independently selected from the group consisting of: light group, tertiary amino group, halo, cyano, epoxy, carboxylic acid, alkane Oxy, alkynyl having 1 to 32 carbon atoms, aryl, alkenyl having 2 to 32 carbon atoms, alkynyl having 2 to 32 carbon atoms, saturated carbocyclic ring having 3 to 14 carbon atoms Unsaturated carbocyclic ring with 3 to 14 carbon atoms, aromatic carbocyclic ring with 6 to 14 carbon atoms, saturated heterocyclic ring with 3 to 14 carbon atoms, Unsaturated heterocycles and aromatic carbon (hetero) rings with 3 to 14 carbon atoms. 34 · —Micro Condensation according to Item 33 of Patent Application Scope Stabilized by Crosslinking-57- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 558558 C8 ~~ ------------ VI. Patent Application Glue 'wherein the cross-linking functional group is an allyl unit. 35. A microgel according to item 33 of the scope of patent application 'which is stabilized by a parent link, wherein the cross-linking functional group is an epoxy-based unit. 〇 ·· A microgel produced according to the method i of the scope of patent application. 37. The microgel according to claim 1, wherein the microgel has a particle size of 10 nm to 1000 nm. 38. The microgel according to item% of the applied patent garden, wherein the microgel has a particle size of 20 nanometers to nanometers. y 39. The method according to item 1 of the patent application scope, further comprising: adding material to be encapsulated in step (ii); and encapsulating the material in the microgel. 40. A method according to item 39 of the application, wherein the material is partially dissolved, dissolved or suspended in a carrier. 41. The method according to item 39 of the scope of patent application, further comprising separating the microgel from the dispersion medium. 42. The method according to item 39, 40, or 4m of the scope of patent application, wherein the material is an organic molecule, a dye molecule, an organic pigment, an inorganic pigment, a catalyst, an aluminum powder, a talc powder, a fiber, a foam, a toxic molecule , Biocides, herbicides, pesticides, pharmaceutical molecules, bioactive materials or genetic materials. 43 · —A microgel containing materials produced according to the method of item 39, 40 or 41 of the scope of patent application. 44. The microgel according to item 43 of the patent application, wherein the material is a pharmaceutical or other biologically active substance. -58- This paper size applies to China National Standard (CNS) A4 (210 X 297g) • n n 1 · • Μι. »Ί! Installed (please read the note on the back before filling in this page) ---- Order ---------- 558558 A8 B8 C8 D8 2. The application scope of the patent is 45.2. The microgel of the application scope is 43. The material is a dye. 46. According to the method of the application scope of the patent application, 1, 39 or 41, it further includes adding the microgel to the coating. combination. I 47. The method according to claim 1, 38, or 41, which further comprises adding the microgel to an injection molding compound to improve impact resistance. 48. The method according to item 47 of the application, wherein the injection molding compound is a thermoplastic resin or a thermosetting resin. 49. A coating composition produced according to method 46 of the scope of patent application. 50. A molded article produced by a method according to item 47 or 48 of the scope of patent application. (Please read the precautions on the back before filling this page) ---------- Order --------- ^ 9. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-59- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)